Method for protecting plants against insects with mixed sulfite esters of alkynyl alcohols and glycol ethers



United States Patent This application is a division of our applicationSerial No. 218,090, filed August 20, 1962, now US. Patent 3,179,682which is a continuation-impart of our application Serial No. 131,741.filed August 16, 1961, now abandoned.

This invention relates to new chemicals, namely new organic esters ofsulfurous acid, more particularly to mixed sulfite esters of alkynylalcohols and glycol ethers.

The new compounds of the present invention are useful as insecticides,particularly for the control of mites.

They may also be used as plasticizers.

The chemicals of the present invention may be represented by the generalformula in which R is an aromatic radical, e.g. phenyl, or naphthyl, ora phenyl or a naphthyl (aryl) radical having one or more substituents inthe aryl nucleus selected from the group consisting of alkyl,cycloalkyl, haloalkyl, alkoxy, nitro and halo; R is an acyclic alkynylradical; n is 2 to '10, and m is 1 to 10. Where m is greater than 1, therepeating oxyalkyl groups may be the same or different. Examples of Rare phenyl, l-naphthyl, 2-naphthyl, p-tolyl, o-tolyl, isopropylphenyl,tert.-butylpheny1, tert.-amyl phenyl, nonylphenyl, cyclohexyphenyl,chloromethylphenyl, methoxyphenyl, nitrophenyl, bromophenyl, 2-chlorophenyl, 2,4-d-ichlorophenyl, trichlorophenyl, pentachlorophenyl.Examples of R are acyclic alkynyl radicals having 3 to carbon atoms,i.e. C,,-H -radicals where n is 3 to 10, e.g. ropargyl, 1-(3-butynyl),2-(3-butynyl), 2-(2-methyl-3-butynyl), l-(2-heptynyl), 1-(3-nonynyl).Examples of the OC,,H --group are ethyleneoxy, trimethyleneoxy,tetramethyleneoxy, propyleneoxy, 1,2-dimethylethyleneoxy.

The prepartion of the chemicals of the invention may be carried out byreacting the selected alkynyl alcohol with the separately preparedchlorosulfinate of the selected glycol ether, which may be made byreacting the selected glycol ether with thionyl chloride. The glycolether which is a. glycol monoether may be made by reacting the selectedphenol, with one to ten moles of the selected alkylene oxide .per moleof the alcohol or phenol. Such prep aration is illustrated by thefollowing reactions with the same symbols R, R and m as in the abovegeneral formula and for convenience using ethylene oxide (n=2) as thealkylene oxide:

3,276,953 Patented Oct. 4, 1966 ice I Reaction (1) above is a well knownand smooth reaction. With one mole of alkylene oxide per mole of phenol,the result will be substantially a single compound containing onealkylene oxide unit. With two or more moles of alkylene oxide per moleof phenol, a mixture of products having varying numbers of alkyleneoxide units is produced. If a compound with a specific number ofalkylene oxide units is desired, the mixture may be fractionated. In thepresent invention for insecticidal uses, it is satisfactory to havemixtures of compounds containing different numbers of alkylene oxideunits from 1 to 10. The following reaction of 'p-treL-butyl .phenolwithpropylene oxide is illustrative of the well known preparation of thestarting glycol ethers according to reaction (1) above:

p-Tert.-butyl phenol (-300 1g., 2.0 moles) and 4 g. sodium hydroxidewere combined and the mixture heated to 150 C. Propylene oxide (279 ml.,232 g., 4.0 males) was added during two hours maintaining the reactiontemperature at 150-160 C. The mixture was cooled, the catalyst wasneutralized with dilute hydrochloric acid, and the product taken up inbenzene. The benzene was removed and the product heated to C. (0.5 mm.)to remove thelast traces of volatile materials. The crude reactionmixture weighed 509 g. (95.7%). It was a mixture of compounds having thestructure uan -Q10 cmzmmon where m== l, 2, 3, 4, 5, etc. The mixture wasdistilled and the following fractions collected:

Percent m=l B.P. 107l28 C. (1 mm.) 32 m=2, B.P. 128-153 C. (1 mm.) 47m=3, B.P. 163184 C. (1 mm.) 14 Residue 7 The preparation of thechlorosulfinat'es of the glycol ethers according to reaction (2) iscarried out at a temperature of between 5 C. and 30 C., preferably near0 C., and the yield of chlorosulfinate is nearly quantitative. An ine'rtsolvent such as benzene, xylene or solvent naphtha may be used. This isillustrated in Example I below.

The preparation of the sulfite esters is carried out in the presence ofan HCl acceptor, such as pyridine, dimethyl aniline or trimethylamine,and in a solvent such as benzene, xylene or solvent naphtha. Thereaction temperature is generally between 10 C. and 50 C., preferablynear 0 C. This is illustrated in Example I below.

Examples of the sulfite diesters of the present invention are:

Propargyl phenoxyethyl sulfite Propargyl o-toloxyethyl sulfite Propargylm-(mpropyDphenoxyethyl sulfite Propargyl p-tert.-amylphenoxyethylsulfite Propargyl p-chlorophenoxyethyl sulfite Propargyll-na-phthoxyethyl sulfite Propargyl p-tert-butylphenoxyisopropyl sulfitePropargyl p-isopropylphenoxyethyl sulfite nearly odorless and relativelyCalculated S, 9.48%.

3 Propargyl o-tert.-butylphenoxyisopropoxyisopropyl sulfite Propargylm-nitrophenoxydiisopropoxyisopropyl sulfite Propargylp-cyclohexylphenoxyethyl sulfite Propargyl p-chloromethylphenoxyethylsulfite Propargyl p-toloxyoctyl sulfite Propargyl p-methoxyphenoxyethylsulfite 2-(3-butynyl) p-tert.-butylphenoxyethoxyisopropyl sulfite1-(2-butynyl) o-chlorophenoxytriethoxyethyl sulfite 1-(3-l1exynyl)p-isopropylphenoxyhexoxyhexyl sulfite.

' Example I illustrates the preparation of the compounds of the presentinvention.

EXAMPLE I Preparation of propargyl p-tert.-butylphenoxyisopropyl sulfitep-Tert.-butylphenoxyisopropyl chlorosulfinate was prepared asillustrated in reaction (2) above as follows:

p-tert.-butylphenoxyisopropyl alcohol or propylene glycol mono-p-tert.buty phenyl ether (104 g., 0.5 mole) prepared according to reaction (1)as described above was dissolved in 150 ml. benzene and the solution wascooled to C. C. Thionyl chloride (45.4 ml., 74.4 g., 0.625 mole) wasadded dropwise during one hour, maintaining the reaction temperaturebelow 5 C. The mixture was allowed to warm to room temperature and standfor 15 hours. The benzene was evaporated under reduced pres- Yield,141.3 g. (97.3%) of a pale yellow oil'which was stable when stored in arefrigerator.

The propargyl p-tert.-butylphenoxyisopropyl sulfite was prepared asillustrated in reaction (3) above as follows: propargyl alcohol (3.2ml., 3.1 g., 0.055 mole), 4.1 ml. (4.0 g., 0.05 mole) pyridine and 30ml. xylene were combined and the solution cooled to 0 C.-5 C. A solutionof 14.5 g. (0.05 mole) p-ter-t.-butylphenoxyisopropyl chlorosulfinate inml. xylene was added during 10 min.

keeping the reaction temperature below 5 C. The mix-1 ture Was stirredfor /2 hour and was washed twice with.

25 ml. portions of water. The mixture was then stirred for one hour with50 ml. 2 N NaOH. The xylene solution was washed several times withsaturated salt solution until the washings were neutral to pH paper. Thexylene was removed under reduced pressure andthe residue heated to a pottemperature of 140 C.v (0.2 mm.) to remove volatile materials. Theproduct was filtered through Dicalite (a diatomaceous earth filter-aid)giving 13.9 g. (89.7% yield) of an amber-colored oil.

Analysis.-Calculated for C H O S: S," 10.33%. Found: S, 10.58.

Sulfur analyses of other chemicals of the, present invention were:

Propargyl p-tert.-butylphenoxyisopropoxyisopropyl sulfite. Calculated S,8.70%. Found: 8.18%.

Propargyl p tert. butyldiisopropoxyisopropyl sulfite. Calculated S,7.52%. Found: 6.51%.

Propargyl p-tert.amylphenoxyethyl sulfite. Calculated S, 10.33%. Found:9.78%.

Propargyl p-tert.-butylphenoxyisopropoxyisopropyl sulfite. Calculated S,8.70%. Found: 8.61%.

Propargyl p-toloxyisopropyl sulfite. Calculated. S, 11.95%. Found:11.19%.

Propargyl 1-paraisopropylphenoxy-Z-butyl sulfite. Calculated'S, 10.33%.Found: 9.14%.

Propargyl 2-methyl-4-tert. butylphenoxyisopr opyl sulfite. Calculated S,9.89%. Found: 8.72%.

Propargyl 1-paratertiaryamylphenoxy 2 butyl sulfite. Calculated S,9.47%. Found: 8.49%.

Propargyl 3-paratertiarybutylphenoxy 2 butyl sulfite. Calculated S,9.89%. Found: 8.92%.

Propargyl 1-paratertiarybutylphenoxy 2 amyl sulfite.

Found: 8.58%. i

sure at room temperature and the residue was warmed to 35 C. (0.8 mm.)to remove the last traces of solvent.

Propargyl o toloxyisopropoxyisopropyl sulfite. culated S, 9.82%. Found:9.11%.

Propargyl p-tolyloxyisopropoxyisopropyl sulfite. Calculated S, 9.82%.Found: 8.74%.

Propargyl p-isopropylphenoxyethoxyethyl sulfite. Calculated S, 9.82%.Found: 8.99%.

Propargyl p-isopropylphenoxyisopropoxyisopropyl sulfite. Calculated S,9.05%. Found: 8.60%.-

Propargyl 1-(1-paraisopropylphenoxy-2-butoxy)-2-butyl sulfite-Calculated S, 8.42%. Found: 27.60%.

Propargyl 2-methyl-4-tert.-butylphenoxyisopropoxyisopropyl sulfite.Calculated S, 8.38%. Found: 7.74%.

1-(3-butynyl) p-tertaamylphenoxyethyl sulfite. Calculated 8, 988%;Found: 9.89%.

2-(3-butynyl) p-tert-amylphenoxyethyl sulfite. Calculated S, 9.88%.Found: 9.38%.

1-(3-hexynyl) p-tert.-amylphenoxyethyl. sulfite. Calculated S, 9.10%.Found: 8.73%.

2-(3-butynyl) o-tert.-butylphenoxyisopropoxyisopropyl sulfite.Calculated S, 8.38%. Found: 7.57%.

1-(2-butynyl) p-tert.-amylphenoxyethyl sulfite. Calculated S, 9.88%.Found: 8.98%.

2-(2-methyl-3-butynyl) p-tert. butylphenoxyisopropyl sulfite. CalculatedS, 9.48%. Found: 8.64%.

EXAMPLE H This example illustrates the insecticidal activity of thechemicals of the present invention in tests against the larvae of Aedesaegypti L. mosquitoes. Fourth instar larvae were used. These larvaenormally reach this stage in 5 days at F. after hatching.

To 10 mgs. of eachchemical to be tested was added 1 ml. of acetone andml. of water to give a concentration of r 100 parts per million(p.p.m.), and a portion was also diluted to 10 p.p.m.

Twenty-five ml. aliquots, replicated once, of each chemical to be testedat concentrations of 100 p.p.m. and 10 p.p.m; and of checks without thechemical and of plain water checks were placed in test tubes and from 5to 25 larvae were added. The tubes were held at 70 F.

Cal-

in darkness for 72 hours. At the end of this periodthe live and deadlarvae were counted and the percentmortality calculated. All the larvaewere alike in the checks (0% mortality). The percent mortality of thelarvae treated with the chemicals of the present invention is shown inthe following table:

This example illustrates the effectiveness of the chemicals of thepresent invention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4" basketsundergreenhouse conditions at 70 F.75 F. were used. Three plants for a totalof six leaves were in each basket for each test. The tests on thechemicals and checks were replicated once. Aqueous'suspensions of thechemicals were prepared by adding to 0.2 gram of the chemical one drop(0.03 gram) of a commercial surface-active dispersing agent(isooctylpheny-l polyethoxy ethanol) and 1 ml. of acetone, washing-into200 ml. of water agitating to form a dispersion and diluting .with waterto the desired concentrationsiof 1000 p.p.m. and 200 p.p.m.

The plants were sprayed with the dispersions of the V chemicals, at thevarious concentrations and the check plants were sprayed with aqueoussolutions containing surfaceactive agent and acetone without thechemicals. The sprayings throughly wet the upper surface of the leaves.The plants were returned to the greenhouse. The following day (-24 hourslater), rings of an adhesive preparation non-toxic to the organismsrunderv test, such as is used on fly papers and for ringing trees, wereplaced around the borders of the upper surfaces of the leaves torestrict the mites to the upper leaf surface. Mites were transferred tothe thus treated leaves by placing beanleaflets heavily infested withtwo-spotted :adult mites, T etranychus telarius L. within the border ofthe adhesive preparation on the leaves of the plants under test. A countof the number of mites transferred was made the same day. The countsranged from 30,to 30.0 mites on the six leaves. The plants were kept inthe greenhouse for another four days. A final count of the number ofliving mites remaining on the leaves was then made. The percent controlis found by using the formula:

Percent control=l00 1 count hvmg mltes) Percent Control at Chemical1,000 p.p.m. 200 p.p.m.

Prppargyl p-tert.-butylphenoxyisopropyl sul- 99 to Propargylp-tert.-butylphenoxyisopropoxyisopropyl fite 99 Propargylp-tert.-butylphenoxydiisopropoxyisopropyl sulfite 99 90 Propargylp-tert.-amylphenoxyethyl sulfite..- 100 100 Proparg'ylo-tert.-butylphenoxyisopropoxyisopropyl sulfite 100 100 1'(3-Butynyl)p-tert.-amylphenoxyethyl sulte 100 96 2-(3Butynyl)p-tert.-amylphenoxyethyl sulfite 100 99 2-(2-Methyl-3-butynyl)p-tert.-amylphenoxyethyl sulfite 100 84 1-(3-Hexynyl)p-tert.-amylphenoxyethyl sul- 76 to 2-(3-Butyny1)o-tert.-butylphenoxyisopropropoxyisopropyl sulfite 100 73 I-(Z-Butynyl)ptert.-amyl phenoxyethyl sulfifp 100 99 Propargyl p-toloxyisopropylnlfite 78 Pgipargyl l-paraisopropylphenoxy-2butyl 5111- 98 to Propargylp-tert.-amylphenoxyis0propyl sulfite. 100 100 Propargyl1-paratertlarybutylphenoxy-2-butyl sulfite 97 Propargyll-paratertiaryamylphenoxy-2-butyl sulfitP 100 Propargyl3-paratertiarybutylphenoxy-2-butyl sulfite 97 77 Propargyll-paratertiarybutylphenoxy-Z-amyl sulfite 100 Propargylo-toloxyisopropoxyisopropyl sulfite 80 Propargylp-toloxyisopropoxyisopropyl sulfite. 77 Pigapargylp-isopropylphenoxyethoxyethyl sul- 64 to Propargylp-isopropylphenoxyisopropoxyisopropyl sulfite 100 99 Propargyl1-(l-paraisopropylphenoxy-2-butoxy) -2-butyl sulfite 96 Propargyl2-methyl-4-p-tert.-butylphenoxyisopropoxyisopropyl snlfii-P 99 Propargylp-tert.-butylphenoxyethoxyisopropyl mlfitP 99 86 EXAMPLE IV This examplealso illustrates the effectiveness of the chemicals of the presentinvention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4" baskets undergreenhouse conditions at 70 F.-75 F. were used. Two plants for a totalof four leaves were in each basket for each test. These tests on thechemicals were replicated once.

The untreated leaves were ringed with adhesive and 40-50 mites weretransferred to each leaf similarly to Example III.

The plants were then sprayed to thoroughly wet the upper surface of theleaves with aqueous solutions of the chemicals at concentrations of 50p.p.m. and 20 p.p.m. prepared as in Example HI. 7

The plants were allowed to dry and a count of the mites was made. Theplants were kept in the greenhouse for three days. A final count of theliving mites remaining on the leaves was then made. The percent controlis found by the formula used in Example III.

The control of mites by the chemicals of the present invention is shownin the following table:

The chemicals of the present invention may be applied in various mannersfor the control of insects. They may be applied to loci to be protectedagainst insects as dusts when admixed with or adsorbed on powdered solidcarriers, such as the various mineral silicates, e.g. mica, talc,pyrophillite and clays, or as liquids or sprays when in a liquidcarrier, as in solution in a suitable solvent, such as acetone, benzeneor kerosene, or dispersed in a suitable non-solvent medium, for example,water. In protecting plants (the term including plant parts) which aresubject to attack by insects, the chemicals of the present invention arepreferably applied as aqueous emulsions containing a surface-activedispersing agent, which may be an anionic, non-ionic or cationicsurface-active agent. Such surface-active agents are well known andreference is made to US. Patent No. 2,547,724, columns 3 and 4 fordetailed examples of the same. The chemicals of the invention may bemixed with such surface-active dispersing agents, with or without anorganic solvent as insecticidal concentrates for subsequent addition ofwater to make aqueous suspensions of the chemicals of the desiredconcentration. The chemicals of the invention may be admixed withpowdered solid carriers, such as mineral silicates, together with asurface-active dispersing agent so that a wettable powder may beobtained, which may be applied directly to loci to be protected againstinsects, or which may be shaken up with water to form a suspension ofthe chemical (and powdered solid carrier) in water for application inthat form. The chemicals of the pres ent invention may be applied toloci to be protected against insects by the aerosol method. Solutionsfor the aerosol treatment may be prepared by dissolving the chemicaldirectly in the aerosol carrier which is liquid under pressure but whichis a gas at ordinary temperature (e.g. 20 C.) and atmospheric pressure,or the aerosol solution may be prepared by first dissolving the chemicalin a less volatile solvent and then admixing such solution with thehighly volatile liquid aerosol carrier. The chemicals may be usedadmixed with carriers that are active of themselves, for example, otherinsecticides, fungicides or bactericides.

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

1. The method of protecting plants against attack by insects whichcomprises applying to the plants a chemical represented by the formula 0R oonHz..)m-0s 012' in which R is selected from the group consisting ofaryl, alkaryl, cycloalkylaryl, haloalkylaryl, alkoxyaryl, nitroaryl andhaloaryl radicals, said aryl and substituted aryl 7 radicals beingphenyl or naphthyl radicals, R is an acylic alkynyl radical, n is 2 to10, and m is l to 10.

2. The method of protecting plants against attacktby insects whichcomprises applying to the plants propargyl p-tert.-butylphenoxyisopropylsulfite.

3. The method of protecting plants against attack by insects whichcomprises applying to the plants propargylp-tert.-butylphenoxyisopropoxyisopropyl sulfite.

4. The method of protecting plants'against attack by insects whichcomprises applying to the plants propargyl2-methyl-4-tert.-butylphenoxyisopropyl sulfite.

5.-The method of protecting plants against attack by insects whichcomprises applying to the plants propargyl1-paratertiaryamylphenoxy-Z-butyl sulfite.

6. The method of protecting plants against attack by References Cited bythe Examiner UNITED STATES PATENTS 2,435,274 2/1948 Hester 167302,820,808 1/1958 Harris et al 260456 2,955,979 10/ 1960 Van Strien167-30 2,968,667 6/1961 Lawlor 260-456 10 3,035,910 5/1962 Boyack et a1.71-2.6 3,075,835 1/ 1963 Fischer 71--2.6 3,123,460 3/1964 Schafer et a1.712.3 3,124,447 3/1964 Winneman et a1 712.3

l5 JULIAN S. LEVITT, Primary Examiner.

' GEORGE A. MENTIS, Assistant Examiner.

1. THE METHOD OF PROTECTING PLANTS AGAINST ATTACK BY INSECTS WHICHCOMPRISES APPLYING TO THE PLANTS A CHEMICAL REPRESENTED BY THE FORMULA